An intramolecular theory of the mass-independent isotope effect for ozone. II. Numerical implementation at low pressures using a loose transition state

A theory is described for the variation in the rate constants for formation of different ozone isotopomers from oxygen atoms and molecules at low pressures. The theory is implemented using a simplified description which treats the transition state as loose. The two principal features of the theory are a phase space partitioning of the transition states of the two exit channels after formation of the energetic molecule and a small (ca. 15%) decrease in the effective density of states, rho [a "non-Rice–Ramsperger–Kassel–Marcus (RRKM) effect"], for the symmetric ozone isotopomers [B. C. Hathorn and R. A. Marcus, J. Chem. Phys. 111, 4087 (1999)]. This decrease is in addition to the usual statistical factor of 2 for symmetric molecules. Experimentally, the scrambled systems show a "mass-independent" effect for the enrichments delta (for trace) and E (for heavily) enriched systems, but the ratios of the individual isotopomeric rate constants for unscrambled systems show a strongly mass-dependent behavior. The contrasting behavior of scrambled and unscrambled systems is described theoretically using a "phase space" partitioning factor. In scrambled systems an energetic asymmetric ozone isotopomer is accessed from both entrance channels and, as shown in paper I, the partitioning factor becomes unity throughout. In unscrambled systems, access to an asymmetric ozone is only from one entrance channel, and differences in zero-point energies and other properties, such as the centrifugal potential, determine the relative contributions (the partitioning factors) of the two exit channels to the lifetime of the resulting energetic ozone molecule. They are responsible for the large differences in individual recombination rate constants at low pressures. While the decrease in rho for symmetric systems is attributed to a small non-RRKM effect eta, these calculated results are independent of the exact origin of the decrease. The calculated "mass-independent" enrichments, delta and E, in scrambled systems are relatively insensitive to the transition state (TS), because of the absence of the partitioning factor in their case (for a fixed non-RRKM eta). They are compared with the data at room temperature. Calculated results for the ratios of individual isotopomeric rate constants for the strongly mass-independent behavior for unscrambled systems are quite sensitive to the nature of the TS because of the partitioning effect. The current data are available only at room temperature but the loose TS is valid only at low temperatures. Accordingly, the results calculated for the latter at 140 K represent a prediction, for any given eta. At present, a comparison of the 140 K results can be made only with room temperature data. They show the same trends as, and are in fortuitous agreement, with the data. Work is in progress on a description appropriate for room temperature

An intramolecular theory of the mass-independent isotope effect for ozone. I

An intramolecular theory of the unusual mass-independent isotope effect for ozone formation and dissociation is described. The experiments include the enrichment factor, its dependence on the ambient pressure, the ratio of the formation rates of symmetric and asymmetric ozone isotopomers, the enrichment of ozone formed from heavily enriched oxygen isotopes, the comparison of that enrichment to that when the heavy isotopes are present in trace amounts, the isotopic exchange rate constant, and the large mass-dependent effect when individual rate constants are measured, in contrast with the mass-independent effect observed for scrambled mixtures. To explain the results it is suggested that apart from the usual symmetry number ratio of a factor of 2, the asymmetric ozone isotopomers have a larger density of reactive (coupled) quantum states, compared with that for the symmetric isotopomers (about 10%), due to being more "RRKM-like" (Rice–Ramsperger–Kessel–Marcus): Symmetry restricts the number of intramolecular resonances and coupling terms in the Hamiltonian which are responsible for making the motion increasingly chaotic and, thereby, increasingly statistical. As a result the behavior occurs regardless of whether the nuclei are bosons (16O, 18O) or fermions (17O). Two alternative mechanisms are also considered, one invoking excited electronic states and the other invoking symmetry control in the entrance channel. Arguments against each are given. An expression is given relating the mass-independent rates of the scrambled systems to the mass-dependent rates of the unscrambled ones, and the role played by a partitioning term in the latter is described. Different definitions for the enrichment factor for heavily enriched isotopic systems are also considered. In the present paper attention is focused on setting up theoretical expressions and discussing relationships. They provide a basis for future detailed calculations

The Sorghum QTL Atlas: a powerful tool for trait dissection, comparative genomics and crop improvement

Key message: We describe the development and application of the Sorghum QTL Atlas, a high-resolution, open-access research platform to facilitate candidate gene identification across three cereal species, sorghum, maize and rice. Abstract: The mechanisms governing the genetic control of many quantitative traits are only poorly understood and have yet to be fully exploited. Over the last two decades, over a thousand QTL and GWAS studies have been published in the major cereal crops including sorghum, maize and rice. A large body of information has been generated on the genetic basis of quantitative traits, their genomic location, allelic effects and epistatic interactions. However, such QTL information has not been widely applied by cereal improvement programs and genetic researchers worldwide. In part this is due to the heterogeneous nature of QTL studies which leads QTL reliability variation from study to study. Using approaches to adjust the QTL confidence interval, this platform provides access to the most updated sorghum QTL information than any database available, spanning 23 years of research since 1995. The QTL database provides information on the predicted gene models underlying the QTL CI, across all sorghum genome assembly gene sets and maize and rice genome assemblies and also provides information on the diversity of the underlying genes and information on signatures of selection in sorghum. The resulting high-resolution, open-access research platform facilitates candidate gene identification across 3 cereal species, sorghum, maize and rice. Using a number of trait examples, we demonstrate the power and resolution of the resource to facilitate comparative genomics approaches to provide a bridge between genomics and applied breeding. © 2018, Springer-Verlag GmbH Germany, part of Springer Nature

Thermal Degradation of Adsorbed Bottle-Brush Macromolecules: Molecular Dynamics Simulation

The scission kinetics of bottle-brush molecules in solution and on an adhesive substrate is modeled by means of Molecular Dynamics simulation with Langevin thermostat. Our macromolecules comprise a long flexible polymer backbone with $L$ segments, consisting of breakable bonds, along with two side chains of length $N$, tethered to each segment of the backbone. In agreement with recent experiments and theoretical predictions, we find that bond cleavage is significantly enhanced on a strongly attractive substrate even though the chemical nature of the bonds remains thereby unchanged. We find that the mean bond life time decreases upon adsorption by more than an order of magnitude even for brush molecules with comparatively short side chains $N=1 \div 4$. The distribution of scission probability along the bonds of the backbone is found to be rather sensitive regarding the interplay between length and grafting density of side chains. The life time declines with growing contour length $L$ as $\propto L^{-0.17}$, and with side chain length as $\propto N^{-0.53}$. The probability distribution of fragment lengths at different times agrees well with experimental observations. The variation of the mean length $L(t)$ of the fragments with elapsed time confirms the notion of the thermal degradation process as a first order reaction.Comment: 15 pages, 7 figure

Isotopic and spin selectivity of H_2 adsorbed in bundles of carbon nanotubes

Due to its large surface area and strongly attractive potential, a bundle of carbon nanotubes is an ideal substrate material for gas storage. In addition, adsorption in nanotubes can be exploited in order to separate the components of a mixture. In this paper, we investigate the preferential adsorption of D_2 versus H_2(isotope selectivity) and of ortho versus para(spin selectivity) molecules confined in the one-dimensional grooves and interstitial channels of carbon nanotube bundles. We perform selectivity calculations in the low coverage regime, neglecting interactions between adsorbate molecules. We find substantial spin selectivity for a range of temperatures up to 100 K, and even greater isotope selectivity for an extended range of temperatures,up to 300 K. This isotope selectivity is consistent with recent experimental data, which exhibit a large difference between the isosteric heats of D_2 and H_2 adsorbed in these bundles.Comment: Paper submitted to Phys.Rev. B; 17 pages, 2 tables, 6 figure

Single-cell quantification of IL-2 response by effector and regulatory T cells reveals critical plasticity in immune response

The sensitivity of T cells to interleukin-2 (IL-2) can vary by three orders of magnitude and is determined by the surface densities of the IL-2 receptor α subunits.Regulatory T cells inflict a double hit on effector T cells by lowering the bulk IL-2 concentration as well as the sensitivity of effector T cells to this crucial cytokine.This double hit deprives weakly activated effector T cells of pSTAT5 survival signals while having only minimal effects on strongly activated effector cells that express increased levels of the IL-2 receptor.Short-term signaling differences lead to a differential functional in terms of proliferation and cell division: regulatory T cell specifically suppress weakly activated effector T cells even at large numbers; small numbers of strongly activated effector T cells overcome the suppression

Original Research By Young Twinkle Students (ORBYTS): Ephemeris Refinement of Transiting Exoplanets III

We report photometric follow-up observations of thirteen exoplanets (HATS-1 b, HATS-2 b, HATS-3 b, HAT-P-18 b, HAT-P-27 b, HAT-P-30 b, HAT-P-55 b, KELT-4A b, WASP-25 b, WASP-42 b, WASP-57 b, WASP-61 b and WASP-123 b), as part of the Original Research By Young Twinkle Students (ORBYTS) programme. All these planets are potentially viable targets for atmospheric characterisation and our data, which were taken using the LCOGT network of ground-based telescopes, will be combined with observations from other users of ExoClock to ensure that the transit times of these planets continue to be well-known, far into the future

The Journal of Microelectronic Research

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